Treating hydrocarbon oils



June 2, 1936. w. M. STRATFORD 2,043,016

' TREATING HYDROCARBON OILS I Filed Oct. 23, 1925 Application October 2 'This inve'ntion relates to thetre'atm'ent-bf- .hy

. athlyfic i os ie' tn rne z'atiq i e' dt ni h r of and to continuously "maintain the catalyst in son i v V t'eri'alt' efiectfpoly riz'a'tion a por'tion of the gii satii atdjc m nnqs undeqcont uea c 1 tionsiwherebyfa desired degree of polymerization ise s s Y The invention broadly contemplates a process oftreatingl'hydrocarbon oils for' the 'separation unstable unsaturated constituents which in 1 cludespassmg the oil inlvaporfo'rm in contact withvasolid adsorbent catalytic material capable ot.--eifectin polymerisation of themore unstable unsaturated constituents to compounds of higher boiling. point; it also. contemplates. theremoval of the relatively non-volatile polymers from the active surface ofthe catalyst and coincident with their formation bysubjecting the catalyst to the washing andlextracting action of aliquid solvent of the polymers; in order to maintain the catalyst in'an activevstatel :iThe-invention also embraces the'provision of an apparatus adapted for carrying on thetreating process." V

Oneof the'imost important factors in the refining of volatile hydrocarbons, and especially the products-of the cracking or decomposition of hydrocarbon oils. is-theremoval of undesirable unsaturated-compounds. While certain oils may contain-alarge proportion of unsaturated compounds'all'of these are'not necessarily undesirable.- However; there-is usually. present a-small portion of the more highly unsaturated products which, if allowed to remain in the oil, will in time polymerize to form gummy deposits and colored products and this invention is particularly directed toward the removal of such compounds from hydrocarbon oil without appreciable loss of N TE SIIAIZES; 1,;A' rsr- I I n'na rmonrnnooimnouoms .wiiiiaai team, Port ArthuryTex Ja 7 v signog, by mesne assignments, to The T Company, New Xork, N. Y., a. corpora'tio s, 1925, Swain C lainrsi (cr tics-self;

- i 1th. V-JC' y 4 7 other unsaturated products whose-presence is not objectionable.- o 1 '1 z :The -tendenc of unsaturated polymerize-as sgreatly; accelerated: low-contacting inthe'fliquidphasesvith'aesolidadsorbeutcatalyst 5 such'sa's fullerfs earth for activated charcoalsorjthe like. 1 The polymerizing: act-ion; oimuclrpatflilfits is'even'more pronouncedi.when-zzcontacted iwith urated compounds "presentsseveral -difllculties.

In the first place, the tendency is Ion-the catalyst to adsorb thepolymrized products as soon as they are formedandas a-result-whemctive sur- 20 face of thecatalyst'is sofpolsori'edand its activ; ity'so reduced as'to require regeneration by-1aurn- 'ing or the's'ubstitution of new catalyst after-a relatively small quantity" of oil has been treated. which of course greatly increases the expense of 25 treating the oil due "to the cost of handling, recovering and replacing the catalytic material. In order to avoid too frequent handling 'of the catalyst and'shut-downs of apparatus a very large bulk of catalyst, several tons for example, 30 may be usedbut this brings out another important difficulty. .Although the undesirable" and very highly unsaturated compounds'are more readily polymerized than are the unsaturated compounds which are neither-harmful nor un- 35 desirable, the passage of oil vapors containing both types ofcompounds through avery large bulk of catalyst results in an over exposure. to thepolymerizinjg action and the polymerization and resultant loss'of harmless unsaturated compounds which it was not desired to remove from the vapors. Thus it is clearly seen. that the use of large bodies ;of catalytic material to avoid frequent replacement is objectionable in that the 45 vapors are subjected to excessive catalytic activity up to the time when the entire body of catalyst becomes practically spent. In addition such procedure is only a makeshift as the catalyst must still be frequently regenerated or replaced and 50 would not adapt the process to continuous operation.

By the practice of my invention, as is hereinafter more fully set forth and described, it is possible to contact hydrocarbon oil vapors with a solid adsorbent catalyst to effect a regulated and controlled degree of polymerization and separation of undesirable unsaturated compounds from the oil without loss of the harmless and desirable unsaturated compounds. At the same time, the catalyst is maintained in a state of effective activity, avoiding frequent replacement of material and enabling the process to be carried on as a practically continuous operation.

I have discovered that the contact catalyst which is used in the polymerization of unsatulated constituents of hydrocarbon oil vapors may be maintained in an active condition by subjecting the catalyst to the washing action of a solvent of the polymers formed during the treatment of the oil vapors. I have further discovered that the polymerizing action of contact catalytic materials upon unsaturated hydrocarbons in the vapor state is increased as the temperature of the reaction increases, so long as de composition or cracking temperatures are not reached, and also that the tendency of the catalyst to adsorb the heavy non-volatile polymers is decreased with elevated temperatures. Therefor, by the practice of my invention I am enabled to polymerize and remove unsaturated hydrocarbons from hydrocarbon oil vapors by contacting the vapors with a catalyst, controlling the degree of polymerization by maintaining the catalyst at a substantially constant degree of activity and by varying the temperature and the time of contact between the catalyst and the oil vapors. Due to the maintenance of the catalyst in an active state, frequent replacement and handling of the catalyst is avoided.

In its application to the purification. of hydrocarbon oils and particularly to the refining of petroleum distillates, the invention is susceptible of numerous variations. For example, various contact catalysts such as fullers earth, charcoal, mineral gels or the like are available for use in effecting polymerization but due to the fact that the catalyst is maintained in a state of activity, frequent replacement is unnecessary and therefore more expensive artificially prepared catalysts of great activity may be used without materially increasing the ultimate cost of the process. The solvent used in washing and maintaining the catalysts in an active state during the process of purification may consist of a portion of the condensed vapor which has been previously purified by contact with the catalyst or it may consist of any suitable material from an extraneous source, such for example as a relatively non-volatile hydrocarbon or related compound. The process may be carried out under varying degrees of temperature and time of contact between the vapors and the catalyst, as has been mentioned before, and the pressures used may range from below atmospheric to the highest pressures within the capacity of the apparatus. However, in directly applying the invention to the treating of cracked distillates from pressure stills, it will be found advantageous to carry on the process under a superatmospheric pressure as by this means a higher temperature may be maintained in the body of the catalyst while at the same time the solvent is maintained in a substantially liquid state. In addition, an increased pressure effects greater concentration of the vapors at the catalyst surface and thereby promotes polymerization of the unsaturated compounds.

Although any combination of the above variable conditions such as activity of the catalyst, temperature, pressure, and the nature of the solvents, may be used, depending upon the characteristics of the oil to be refined, in order that the invention may be more fully understood I shall proceed to describe a simple and preferred application thereof.

The treatment or purification is preferably carried out directly in connection with a cracking still as a source of vaporized hydrocarbonoil containing objectionable and unstable unsaturated compounds. For example, a cracking still which is operated under a superatrnospheric pressure and which is fitted with a fractionating tower is connected by means of vapor lines.with a container in which is placed a bed of active absorbent material such as fullers earth, activated charcoal or the like. A reflux condenser is arranged to supply reflux to the fractionating column and also to the contact material, as will be more fully discussed hereinafter. During operation of the cracking still, which is preferably continuous, hydrocarbon vapors of practically uniform composition are evolved; the vapors are passed through the fractionating tower and from this point are lediuto the vessel containing the contact material. The contactmaterial will be supported upon a screen ofwire cloth or the like to afford free passage ofthe vapors through and in contact with the .adsorbent material, and the depth of [the bed will vary with the particular type of adsorbent material used and also with the degree of unsaturation of the vapors, which may fluctuate with the variations in the operating conditions of the cracking still.

The vessel containing the contact material will preferably be heavily insulated and will receive a portion of the reflux liquid which is supplied to the fractionating tower from the reflux condenser. An alternative arrangement consists in omitting the insulation on the catalyst container in order that heat will be radiated therefrom suflicient to cause condensation of a portion of the vapors in contact with the catalyst. Thus the fractionated vapors are passing in contact with the catalyst, while a portion of the condensate or reflux is continuously washing out and dissolving the polymers therefrom as fast as they are formed. The solution of polymers washed out of the contact material may be returned to the fractionating column or to the still for separation of the colored non-volatile material from the solvent. The vapors issuing from the treating chamber or vessel are substantially free from objectionable, gum-forming unsaturated hydrocarbons. The catalyst chamber may be placed between the still and the fractionating column in which case the total vapors issuing from the still are subjected to the purifying treatment. However, in most cases it will be found preferable to fractionate the vapors before subjecting them to contact with the catalyst.

Although in the example described above, the solvent used in washing the catalyst consists of the condensed purified hydrocarbon vapors, other suitable solvents may be used for this purpose and it is not intended that this invention should be limited to the use of any one solvent material for this purpose. In addition, under certain conditions it may be desirable to supply the solvent to the catalyst at intervals instead of continuously, or as a modification of this procedure, to supply a relatively small quantity of the solvent to the catalyst continuously and to increase the rate of flow of the solvent at intervals to provide for the more thorough removal of the adsorbed polymers.

In the accompanying drawing is shown, more or less diagrammatically, apparatus within the invention and suitable for carrying on the desired process. In this drawing:

Figure 1 is an elevation partly in central vertical section of a catalyst container, including the necessary connections.

Figure 2 is a view partly in central vertical section and partly in elevation illustrating a specific application of the apparatus shown in Figure 1, including a cracking still, fractionating tower, reflux condenser, etc.

Referring to Figure 1, element l is a vessel or container for the body of catalytic material 2 which rests on the perforated plate 3, allowing a free flow of vapors through the container in contact with the catalyst. Unpurified vapors from any suitable source, for example a still, enter the chamber through the connection at 4 and pass upward through the catalyst 2 during which passage the more highly unsaturated constituents of the vapors are polymerized to compounds of higher boiling point, the bull: of'which condense upon the surface of the catalyst, while the purified vapors pass on through the connection 6 to a condenser (not shown). A solvent of the polymers formed, which are condensed upon the catalyst, is introduced through the pipe 1 and the spray 8, and is distributed thereby over the bed of catalytic material through which it fiows, washing the heavy polymers from the surface of the catalyst and maintaining it in an active condition. The solution of the polymerized hydrocarbons collects in the lower portion of the container I and is withdrawn continuously through the connection 9 and may be returned to the still or treated separately for the recovery of the solvent and of the polymers which, due to their chemical and physical properties, may be of value in the manufacture of synthetic chemicals and the like.

In Figure 2, which illustrates an application of the apparatus shown in Figure 1, l0 represents a still for cracking hydrocarbon oil at elevated temperatures and pressures, said still being fitted with a suitable fractionating tower i I, fitted with a connection l2 for returning condensate to the still. The still l0 may be supplied with suitable connections (not shown) for supplying fresh oil and withdrawing residual oil in order that the distillation may be carried on continuously. The vapors from the fractionating tower ll enter the catalyst container 1 through the vapor line 4 and pass upwards through the catalytic material 2 where purification of the vapors and polymerization of the unstable unsaturated constituents takes place. The purified vapors pass from the catalytic chamber I through the line 6 to a reflux condenser I3 where a portion of the vapors are condensed, the remainder being passed to the main condenser I4 where condensation takes place after which separation of the condensate and fixed gases is accomplished in the receiving drum The condensate from the reflux condenser l3 fiows through the line l6 to the T H where it is divided into two portions, one of which is directed through the line i8 to the upper portion of the fractionating tower l I, while the other portion is directed through the line I and the spraying device 8 to the bed of catalytic material 2 in the catalyst container l. Thus a portion of the condensed purified hydrocarbons is supplied to the catalyst to act as a solvent of the polymers formed and adsorbed upon the surface of the catalyst. After passing downward through the bed of catalytic material, this portion of the condensate from the reflux condenser, which now contains dissolved polymers, collects in the lower portion of the container l and flows through the line 9 to the still I0 or 'to any desired point in the tower ll, l the point of entry to the tower or to the still being controlled by means of the valves l9a, I92), I90, and "id.

Although for the sake of convenience and clearness, the apparatus has been described in connec- 1 tion with a simple type of still adapted for pressure distillation, the process and apparatus may be operated in conjunction with any other cracking process, either vapor or liquid phase, yielding products of approximately the boiling range of 2 gasoline which contain undesirable unsaturated compounds.

Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope 2 thereof, and therefore, only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. In apparatus for treating hydrocarbon oils, 3 a still, a fractionating tower in vapor communication therewith, a refiux condenser, a catalyst container positioned between and in vapor communication with said fractionating tower and reflux condenser, a bed of pulverulent solid catalytic material positioned therein, means for supplying to the bed of catalytic material a portion of the condensate from the reflux condenser, means for supplying the remainder of the condensate from the reflux condenser to the upper portion of the fractionating tower, means for introducing into the fractionating tower the condensate from the catalyst chamber, means for returning the condensate from the lower portion of the fractionating tower to the still. 45

2. The process of treating cracked petroleum vapors, including vapors of constituents boiling within a gasoline boiling-point range, to remove undesirable gum-forming compounds therefrom, which comprises passing a stream of said vapors through a fractionating zone and therein progressively fractionating said vapors to obtain vapors of a desired end point, while condensing and separating higher-boiling constituents, subjecting the resultant vapors to contact with solid adsorbent catalytic material in a treating zone to effect polymerization of undesirable gum-forming constituents to products having boiling-points higher than that of the desired gasoline product, removing resultant polymer-containing oil from said treating zone and returning at least a portion thereof to a point in said fractionating zone as reflux, removing treated vapors from said treating zone, recovering therefrom a liquid condensate containing c'onstituents boiling within a gasoline boiling-point range, and returning at least a portion of said condensate to a later point in said fractionation zone as reflux.

3. The process of treating cracked petroleum vapors, including vapors of constituents boiling within a gasoline boiling-point range, to remove undesirable gum-forming compounds therefrom, which comprises passing a stream of said vapors through a fractionating zone and therein progressively fractionating said vapors to obtain vapors of a desired end point, While condensing and separating higher-boiling constituents, subjecting the resultant vapors to contact with solid adsorbent catalytic material in a treating zone to eiiect polymerization of undesirable gumJorm'ing constituents to products having boiling-points higher than that of the desired gasoline product. removing resultant polymer-containing oil from said treating zoneand returning at least a portion hereof to a point in said fractionating zone as reflux, removing treated vapors from said treating zone, subjecting said treated vapors to partial condensation to recover therefrom a condensate comprising constituents'boiling Within a gasoline boiling-point range; returning at least a portion of'said condensate to a later point in said fractionation zone as reflux, and finally condensing the remainding vapors to recover the desired treated product.

v WILLIAM M. STRA'IFORD. w 

